CN102086152A - Method for producing trifluoroacetic acid methyl ester by catalytic oxidation of methane - Google Patents
Method for producing trifluoroacetic acid methyl ester by catalytic oxidation of methane Download PDFInfo
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- CN102086152A CN102086152A CN200910241378XA CN200910241378A CN102086152A CN 102086152 A CN102086152 A CN 102086152A CN 200910241378X A CN200910241378X A CN 200910241378XA CN 200910241378 A CN200910241378 A CN 200910241378A CN 102086152 A CN102086152 A CN 102086152A
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- trifluoroacetic acid
- methane
- trifluoro
- acetate
- methyl hydride
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Abstract
The invention provides a method for producing trifluoroacetic acid methyl ester by catalytic oxidation of methane, belonging to the technical field of chemical industry. The method is characterized in that in a mixing solvent composed of perfluoroctane or perfluornonane and trifluoroacetic acid, methane is subjected to catalytic oxidation to obtain the trifluoroacetic acid methyl ester by taking oxygen as oxidant and using palladium acetate, benzoquinone and phospho vando molybdic acid as catalysts. In the method, the volume ratio of perfluoroctane or perfluornonane to trifluoroacetic acid is 1:1 to 1:10; the total pressure of methane and oxygen is 2.0-5.0 MPa, and the partial pressure ratio of methane to oxygen (1.6-10):1; and reaction is carried out for 1-12 hours at the temperature of 40-120 DEG C to produce the trifluoroacetic acid methyl ester. Compared with the method using single solvent trifluoroacetic acid, the method provided by the invention has the advantage of obviously improved yield of trifluoroacetic acid methyl ester.
Description
Technical field
The present invention relates to the method that trifluoro-acetate is produced in a kind of methyl hydride catalyzed oxidation, belong to chemical technology field.
Background technology
Shortage day by day along with petroleum resources further develops natural gas source and more and more causes people's attention.The main component of Sweet natural gas is a methane, and the comprehensive utilization of methane can be divided into direct conversion method and indirect reformer method two big classes.Directly conversion method is methane to be converted into liquid products such as acid, aldehyde, alcohol.At present, production technique mostly is the indirect reformer method, promptly adopts the method for steam cracking to produce synthetic gas (CO+H
2), produce liquid products such as acid, aldehyde, alcohol by F-T synthesis reaction by synthetic gas again.But methane conversion is that the process energy consumption of synthetic gas is very high, therefore presses for the direct catalyzed oxidation novel method of methane under the exploitation lesser temps.
In recent years, people have proposed the effective catalyst of the direct catalyzed oxidations of some methane.Up to now, the most effective catalyzer be with the connection pyrimidine (bmpy) be platinum complex catalyst Pt (bpym) Cl of part
2This catalyzer can be at a lower temperature with the methyl hydride catalyzed methyl sulfate that is oxidized in 102% oleum, the methyl sulfate hydrolysis can obtain methyl alcohol (R.A.Periana, D.J.Taube, S.Gamble, et al.Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative.Science, 1998,280 volumes, 560～564 pages).But this catalyzer costs an arm and a leg, and the moisture content that reaction process generates significantly descends catalyst activity, brings very big difficulty to industrial application.
In the direct catalytic oxidation process of methane, need strong oxidizer usually, as the vitriol oil, K
2S
2O
8Or H
2O
2Oxygen is a kind of cheapness, environmental friendliness oxygenant, has very strong magnetism, but still less with the research of dioxygen oxidation methane.
Reaction solvent also has a significant impact the direct catalytic oxidation process of methane.Seki etc. have compared trifluoroacetic anhydride, the methyl nitrile, methane conversion in water and the dimethyl sulfoxide (DMSO), wherein methane conversion is the highest in the trifluoroacetic anhydride, and do not detect methyl alcohol and derivative (Y.Seki thereof in water and the dimethyl sulfoxide (DMSO), N.Mizuno, M.Misono.High-yield liquid-phase oxygenation of methane with hydrogen peroxide catalyzed by 12-molybdovanadophosphoric acid catalyst precursor.Applied Catalysis A:General, 1997,158 volumes, the L47-L51 page or leaf).Solvent commonly used has the vitriol oil (or oleum), trifluoroacetic acid (or trifluoroacetic anhydride).The vitriol oil (or oleum) provides the strong oxidizing property environment, can suppress transition metal ion and be reduced to simple substance and inactivation, and help to form stable intermediate, and further be decomposed into methyl sulfate.Trifluoroacetic acid (or trifluoroacetic anhydride) is made solvent, helps to form the stable product trifluoro-acetate.
Summary of the invention
The invention provides the method that trifluoro-acetate is produced in a kind of methyl hydride catalyzed oxidation, it is characterized in that: in the mixed solvent of PFO or Perfluorononane and trifluoroacetic acid composition, with oxygen is oxygenant, palladium, benzoquinones and molybdovanaphosphoric acid are catalyzer, with the methyl hydride catalyzed trifluoro-acetate that is oxidized to.
This method may further comprise the steps: palladium, benzoquinones and molybdovanaphosphoric acid are added by a certain percentage in the mixed solvent of PFO or Perfluorononane and trifluoroacetic acid composition, wherein the volume ratio of PFO or Perfluorononane and trifluoroacetic acid is 1: 1～1: 10; Feeding total pressure is methane and the oxygen of 2.0～5.0MPa, and wherein the intrinsic standoff ratio of methane and oxygen is (1.6～10): 1; Stir,, generate trifluoro-acetate at 40～120 ℃ of isothermal reaction 1～12h.
Compare with adopting the trifluoroacetic acid single solvent, the present invention adopts mixed solvent can significantly improve the productive rate of trifluoro-acetate.
Embodiment
Comparative Examples
At first with 0.67mg palladium (0.30mM), 1.30mg benzoquinones (1.20mM) and 0.87mg molybdovanaphosphoric acid H
5PMo
10V
2O
40(0.05mM) place in the stainless steel autoclave (50mL) that glass-lined is housed, wherein reaction solvent is the 10mL trifluoroacetic acid, the envelope still.Get rid of air in the still with methane, feed 2.5MPa methane and 0.5MPa oxygen at last, close intake valve, react 8h down and under the magnetic agitation at 80 ℃.After reaction stops, placing mixture of ice and water to be cooled to about 3 ℃ autoclave, take out reaction solution, utilize gas chromatograph to analyze the concentration of trifluoro-acetate in the liquid phase.The concentration that records trifluoro-acetate is 0.91mM.
Embodiment 1
The concentration of palladium, benzoquinones, molybdovanaphosphoric acid and operating process and Comparative Examples are identical, and wherein reaction solvent is 10mL trifluoroacetic acid and 2mL PFO.Subsequent step and Comparative Examples are identical.After reaction stopped, the concentration that records trifluoro-acetate was 3.77mM.
Embodiment 2
The concentration and the Comparative Examples of palladium, benzoquinones, molybdovanaphosphoric acid are identical, and the add-on of trifluoroacetic acid and PFO and operating process and embodiment 1 are identical.Feed 2.5MPa methane and 1.5MPa oxygen, close intake valve.Subsequent step and Comparative Examples are identical.After reaction stopped, the concentration that records trifluoro-acetate was 4.54mM.
Embodiment 3
The concentration of palladium, benzoquinones, molybdovanaphosphoric acid and operating process and Comparative Examples are identical, and wherein reaction solvent is 10mL trifluoroacetic acid and 3mL PFO.Subsequent step and Comparative Examples are identical.After reaction stopped, the concentration that records trifluoro-acetate was 10.66mM.
Embodiment 4
The concentration of palladium, benzoquinones, molybdovanaphosphoric acid and operating process and Comparative Examples are identical, and wherein reaction solvent is 10mL trifluoroacetic acid and 5mL PFO.Subsequent step and Comparative Examples are identical.After reaction stopped, the concentration that records trifluoro-acetate was 17.72mM.
Claims (7)
1. method that trifluoro-acetate is produced in methyl hydride catalyzed oxidation, it is characterized in that: in the mixed solvent of PFO or Perfluorononane and trifluoroacetic acid composition, with oxygen is oxygenant, and palladium, benzoquinones and molybdovanaphosphoric acid are catalyzer, with the methyl hydride catalyzed trifluoro-acetate that is oxidized to; Compare with adopting the trifluoroacetic acid single solvent, adopt mixed solvent can significantly improve the productive rate of trifluoro-acetate.
2. the method for trifluoro-acetate is produced in methyl hydride catalyzed oxidation according to claim 1, and it is characterized in that: in mixed solvent, the volume ratio of PFO or Perfluorononane and trifluoroacetic acid is 1: 1～1: 10.
3. the method for trifluoro-acetate is produced in methyl hydride catalyzed oxidation according to claim 1, and it is characterized in that: be oxygenant with oxygen, palladium, benzoquinones and molybdovanaphosphoric acid are catalyzer, with the methyl hydride catalyzed trifluoro-acetate that is oxidized to.
4. the method for trifluoro-acetate is produced in methyl hydride catalyzed oxidation according to claim 1, it is characterized in that: molybdovanaphosphoric acid is the molybdovanaphosphoric acid of the Keggin structure of 1～4 vanadium atom replacement.
5. the method for trifluoro-acetate is produced in methyl hydride catalyzed oxidation according to claim 1, and it is characterized in that: the initial total pressure of methane and oxygen is 2.0～5.0MPa, and the intrinsic standoff ratio of methane and oxygen is (1.6～10): 1.
6. the method for trifluoro-acetate is produced in methyl hydride catalyzed oxidation according to claim 1, and it is characterized in that: the temperature of reaction system is 40～120 ℃.
7. the method for trifluoro-acetate is produced in methyl hydride catalyzed oxidation according to claim 1, and it is characterized in that: the reaction times is 1～12h.
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| CN 200910241378 CN102086152B (en) | 2009-12-08 | 2009-12-08 | Method for producing trifluoroacetic acid methyl ester by catalytic oxidation of methane |
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| CN 200910241378 CN102086152B (en) | 2009-12-08 | 2009-12-08 | Method for producing trifluoroacetic acid methyl ester by catalytic oxidation of methane |
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| CN102086152B CN102086152B (en) | 2013-06-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747847A (en) * | 2020-06-29 | 2020-10-09 | 中山大学 | Method for alkane selective catalytic oxidation reaction |
| KR20210098002A (en) * | 2020-01-31 | 2021-08-10 | 한국과학기술연구원 | Catalysts for methane activation and manufacturing method of methylestare using the same |
| CN113248374B (en) * | 2020-02-07 | 2023-09-29 | 韩国科学技术研究院 | Method for preparing high-purity methanol precursor, methanol and methyl ester from methane |
Citations (3)
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|---|---|---|---|---|
| US20060167314A1 (en) * | 2004-07-19 | 2006-07-27 | Periana Roy A | Process for converting methane to acetic acid |
| CN101209956A (en) * | 2006-12-25 | 2008-07-02 | 汉能科技有限公司 | Method for preparing menthol by directly oxidizing liquid-phase methane |
| CN101495435A (en) * | 2006-07-04 | 2009-07-29 | 中国科学院大连化学物理研究所 | Oxiadition catalyst |
-
2009
- 2009-12-08 CN CN 200910241378 patent/CN102086152B/en not_active Expired - Fee Related
Patent Citations (3)
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|---|---|---|---|---|
| US20060167314A1 (en) * | 2004-07-19 | 2006-07-27 | Periana Roy A | Process for converting methane to acetic acid |
| CN101495435A (en) * | 2006-07-04 | 2009-07-29 | 中国科学院大连化学物理研究所 | Oxiadition catalyst |
| CN101209956A (en) * | 2006-12-25 | 2008-07-02 | 汉能科技有限公司 | Method for preparing menthol by directly oxidizing liquid-phase methane |
Non-Patent Citations (3)
| Title |
|---|
| TAKAHIRO YOKOTA,SHINYA FUJIBAYASHI,YUTAKA NISHIYAMA: "Molybdovanadophosphate(NPMoV)/hydroquinone/ O2 system as an efficient reoxidation system in palladium-catalyzed oxidation of alkenes", 《JOURNAL OF MOLECULAR CATALYSIS A:CHEMICAL》 * |
| 曾毓华: "《氟碳表面活性剂》", 30 June 2001 * |
| 石晓波，石淑华，李春根，李苑: "Keggin结构磷钼钒酸盐纳米催化剂的合成及其催化性能", 《功能材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210098002A (en) * | 2020-01-31 | 2021-08-10 | 한국과학기술연구원 | Catalysts for methane activation and manufacturing method of methylestare using the same |
| KR102405065B1 (en) | 2020-01-31 | 2022-06-07 | 한국과학기술연구원 | Catalysts for methane activation and manufacturing method of methylestare using the same |
| CN113248374B (en) * | 2020-02-07 | 2023-09-29 | 韩国科学技术研究院 | Method for preparing high-purity methanol precursor, methanol and methyl ester from methane |
| CN111747847A (en) * | 2020-06-29 | 2020-10-09 | 中山大学 | Method for alkane selective catalytic oxidation reaction |
| CN111747847B (en) * | 2020-06-29 | 2021-07-16 | 中山大学 | Method for alkane selective catalytic oxidation reaction |
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